CN106486662A - The preparation method of carbon-coated lithium ion battery negative material - Google Patents
The preparation method of carbon-coated lithium ion battery negative material Download PDFInfo
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- CN106486662A CN106486662A CN201611127237.1A CN201611127237A CN106486662A CN 106486662 A CN106486662 A CN 106486662A CN 201611127237 A CN201611127237 A CN 201611127237A CN 106486662 A CN106486662 A CN 106486662A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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Abstract
The present invention relates to a kind of preparation method of carbon-coated lithium ion battery negative material, belong to technical field of lithium ion.It adopts three kinds of different process that carbon coating negative material is obtained, and its chemical formula is Li4Ti5O12/C.Wherein in order to prevent a small amount of volatilization of lithium under high-temperature calcination, the amount excessive 5% of the material of lithium；Weigh solubility lithium source, titanium dioxide, carbon source according to mol ratio, after different process mix homogeneously, add appropriate distilled water or ethanol to stir, obtain rheology phase.After rheology is added heated drying, calcine through once or twice, after grinding, obtain described carbon-coated lithium ion battery negative material Li4Ti5O12/C.Than uncoated material, battery capacity is further lifted the carbon-coated lithium ion battery negative material of present invention synthesis, with carbon-coated lithium ion battery negative material Li4Ti5O12Also electric conductivity and the high rate capability of material can effectively be improved.
Description
Technical field
The present invention relates to a kind of preparation method of carbon-coated lithium ion battery negative material, belong to lithium ion battery technology neck
Domain.
Background technology
Lithium ion battery has the advantages that specific energy is big, self discharge is little, has extended cycle life, has a safety feature because of it, by
It is widely used in various mobile electronic equipments and high-energy device, such as smart mobile phone, notebook and electric automobile etc..
In lithium ion battery material, carbon becomes current commodity lithium ion battery with its cheap price and preferable safety
Main negative material.Although Carbon anode is widely used, Carbon anode initial charge can form solid on carbon granule surface
Body dielectric film（SEI）Cause battery capacity to lose, and SEI growing amount increases with the increase of charge and discharge cycles number of times, simultaneously
The anti-increasing of the internal resistance of cell, specific energy and power-performance reduce.Furthermore, because the current potential of carbonaceous electrodes current potential and lithium is very close to high power
Easily generate lithium coating in activated carbon particle surface during rate quick charge, or even form Li dendrite and cause cell safety sex chromosome mosaicism.By
Limit application in terms of power battery material for the carbon negative pole material in various reasons.
And the lithium titanate of spinel structure（Li4Ti5O12）Negative material, as a kind of " zero strain " material, in discharge and recharge
During structure highly stable, cycle performance is excellent；There is very stable charging/discharging voltage platform, existing almost without voltage delay
As；Do not react with electrolyte, low price, easily prepare.Compared with carbon negative pole material, it can overcome many graphite-based electricity
The shortcoming that pond shows：⑴ Li4Ti5O12The side reaction existing for Carbon anode can be eliminated and suppress SEI passivating film to be formed；⑵
At 25 DEG C, Li4Ti5O12Electrochemical diffusion coefficient（2×10-8cm2/s）A number bigger than the diffusion coefficient in carbon negative pole material
Magnitude, high diffusion coefficient allows that this negative material is quick, multi cycle discharge and recharge；⑶ Li4Ti5O12In charge and discharge process
In can avoid because of Lithium-ion embeding and the volumetric expansion that causes of abjection and the electrode structure caused by shrinking damages, substantially increase
The cycle performance of battery.(4) electrode potential is higher, can prevent the Li dendrite that material with carbon element occurs as li-ion electrode materials
Phenomenon, safety issue is greatly improved.Therefore lithium titanate with spinel structure（Li4Ti5O12）Negative material is expected to as new
The negative material of generation lithium-ion-power cell.
Although lithium titanate anode material has many advantages, the specific capacity of lithium titanate and other negative materials compared with Carbon anode
Compare much lower, theoretical specific capacity is 175mAh/g, and relatively low as its tap density of battery material also ratio, electric conductivity is poor.Institute
Widely being paid close attention to also result in its study on the modification in recent years, such as the works such as Surface coating and doping vario-property being carried out to it
Make.
Content of the invention
It is an object of the invention to solving existing lithium ion battery negative material Li4Ti5O12Capacity is relatively low, poorly conductive
Problem, and lift the high rate capability of battery further.Provide three kinds and prepare carbon-coated lithium ion battery negative material
Li4Ti5O12The method of/C, by surface coated method, can increase substantially the original chemical property of material.
The technical scheme providing according to the present invention, the preparation method of carbon-coated lithium ion battery negative material, step is as follows：
（1）The preparation of rheology phase：Molal quantity by the lithium of lithium salts：Titanium dioxide in molar ratio 4.05～4.15：5～5.05 take thing
Material, mix homogeneously, add lithium salts and titanium dioxide gross mass in 3%～6% solvent, grind pulp together, obtain rheology phase；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in air dry oven, dry under the conditions of 80～120 DEG C
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）The preparation of presoma：Solid product is placed in Muffle furnace and is calcined, programming rate is 5 DEG C/min, is warming up to
400～600 DEG C, calcine 4～6 hours, obtain presoma；
（4）The preparation of negative material：Presoma is cooled to and grinds 0.5～1 hour in mortar machine after room temperature, after grinding before
Drive body compacting after be placed in Muffle furnace, in excess oxygen or air atmosphere under calcined, programming rate be 3～8 DEG C/
Min, is warming up to 600～900 DEG C, calcines 6～10 hours, the lithium ion battery negative material obtaining after being cooled to room temperature
Li4Ti5O12；
（5）The covert preparation of Secondary Flow：By step（4）Obtained negative material Li4Ti5O12With carbon source according to mass ratio 10～
10.15:1～1.25 mix homogeneously, is subsequently added Li4Ti5O12With the solvent of carbon source gross mass 5%～10%, grind to form together
Pulpous state, obtains Secondary Flow covert；
（6）The preparation of secondary solid-phase product：By step（5）Gained Secondary Flow is in a disguised form placed in air dry oven in 80～120 DEG C
Lower drying 10～12 hours, to evaporate expeling solvent, obtains secondary solid-phase product；
（7）Secondary clacining：By step（6）Gained secondary solid-phase product is placed in Muffle furnace to be calcined, programming rate be 5 DEG C/
Min, is warming up to 600～800 DEG C, calcines 1～2 hour, product is cooled to after room temperature and grinds 0.5～1 hour in mortar machine,
Obtain final product described carbon-coated lithium ion battery negative material Li4Ti5O12/C.
The preparation method of carbon-coated lithium ion battery negative material, step is as follows：
（1）The preparation of rheology phase：Take titanium dioxide and carbon source according to mass ratio 10～10.15:1～1.25 feeding, mix homogeneously,
Add the solvent of titanium dioxide and carbon source gross mass 3%～6%, grind pulp together, obtain rheology phase；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in dry under the conditions of 80～120 DEG C in air dry oven
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）Calcining：By step（2）Gained solid product is placed in Muffle furnace to be calcined, and programming rate is 5 DEG C/min, heats up
To 600～800 DEG C, calcine 1～2 hour, product is cooled to after room temperature and grinds 0.5～1 hour in mortar machine, obtain final product carbon bag
Cover material TiO2/C；
（4）The covert preparation of Secondary Flow：Molal quantity by lithium in lithium salts：Carbon encapsulated material TiO2/ C mol ratio be 4.05～
4.15:5～5.05 mix homogeneously, add lithium salts and carbon encapsulated material quality in 3%～6% solvent, grind pulp together, obtain
Covert to Secondary Flow；
（5）The preparation of secondary solid-phase product：Rheology phase is placed in air dry oven and is dried 10～12 under the conditions of 80～120 DEG C
Hour, to evaporate expeling solvent, obtain secondary solid-phase product；
（6）Secondary clacining：Secondary solid-phase product is placed in Muffle furnace, in excess oxygen or air atmosphere under forged
Burn, programming rate is 3～8 DEG C/min, is warming up to 600～900 DEG C, calcine 8～16 hours, product is cooled to after room temperature and is grinding
Described carbon-coated lithium ion battery negative material Li is obtained after grinding 0.5～1 hour in alms bowl machine4Ti5O12/C.
The preparation method of carbon-coated lithium ion battery negative material, step is as follows：
（1）The preparation of rheology phase：In molar ratio 4.05～4.15:5～5.05：0.05 by the molal quantity of the lithium of lithium salts, titanium dioxide
Titanium and carbon source mix homogeneously, add reactant gross mass in 3%～6% solvent, grind pulp together；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in dry under the conditions of 80～120 DEG C in air dry oven
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）Calcining：By step（2）Gained solid product is placed in Muffle furnace, in excess oxygen or air atmosphere under carry out
Calcining, programming rate be 3～8 DEG C/min, be warming up to 600～900 DEG C, calcine 8～16 hours, by product be cooled to after room temperature
Described carbon-coated lithium ion battery negative material Li is obtained after grinding 0.5～1 hour in mortar machine4Ti5O12/C.
Described solvent is water, ethanol or propanol.
Described carbon source is one of polyvinyl alcohol, carbamide, sucrose or citric acid.
Described lithium salts is one kind of lithium nitrate, lithium carbonate or Lithium hydrate.
Beneficial effects of the present invention：The present invention uses the Li of carbon coating preparation4Ti5O12/ C negative material granule is uniform, is
Spinel structure, degree of crystallinity is high, and the stability of material improves（2）The carbon-coated lithium ion battery negative material of synthesis is than uncoated
Material, battery capacity further lifted（3）Carbon-coated lithium ion battery negative material also can effectively improve material
Electric conductivity and high rate capability.
Brief description
Fig. 1 is the negative material Li of embodiment 1 preparation4Ti5O12XRD figure.
Fig. 2 is the negative material Li of embodiment 1 preparation4Ti5O12SEM figure.
Fig. 3 is carbon coating Li of embodiment 2 preparation4Ti5O12The first charge-discharge curve of/C negative material（1.0～3.0V,
0.1C, room temperature）.
Fig. 4 is carbon coating Li of embodiment 3 preparation4Ti5O12The first charge-discharge curve of/C negative material（1.0～3.0V,
0.1C, room temperature）.
Fig. 5 is carbon coating Li of embodiment 4 preparation4Ti5O12The first charge-discharge curve of/C negative material（1.0～3.0V,
0.1C, room temperature）.
The abscissa of Fig. 1 is sweep limitss 2 θ（10～90 °）, vertical coordinate is the intensity at peak.The amplification of Fig. 2 is
30000 times.The abscissa of Fig. 3 is specific capacity, mAh/g, and vertical coordinate is voltage, and unit is V, and in Fig. 3, curve A refers to the song that charges
Line, curve B refers to discharge curve.The abscissa of Fig. 4 is specific capacity, mAh/g, and vertical coordinate is voltage, and unit is V, curve in Fig. 4
A refers to charging curve, and curve B refers to discharge curve.The abscissa of Fig. 5 is specific capacity, mAh/g, and vertical coordinate is voltage, and unit is
In V, Fig. 5, curve A refers to charging curve, and curve B refers to discharge curve.
Specific embodiment
With reference to embodiment, technical scheme is described further.
Embodiment 1
（1）Lithium carbonate, nano titanium oxide are in molar ratio 2.025:5（Wherein in order to prevent a small amount of of lithium under hot environment
Volatilization, lithium carbonate excessive 5%）, after grinding to form fine particle respectively, mix homogeneously in big mortar, add appropriate anhydrous second
Alcohol, continues to grind 0.5 hour until mixture becomes homogeneous rheology phase.
（2）Rheology phase is placed in air dry oven and is dried 11 hours under the conditions of 100 DEG C, to evaporate expeling solvent, obtain
To solid product；
（3）Solid product is placed in Muffle furnace and is calcined, programming rate is 5 DEG C/min, is warming up to 500 DEG C, calcining 4 is little
When, obtain presoma；
（4）Presoma grinds 0.5 hour after being cooled to room temperature in mortar machine, is placed in Muffle after the presoma compacting after grinding
In stove, in excess oxygen or air atmosphere under calcined, programming rate is 5 DEG C/min, is warming up to 800 DEG C, and calcining is 8 little
When, the lithium ion battery negative material Li obtaining after being cooled to room temperature4Ti5O12.
The negative material that embodiment 1 is obtained is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, with METHYLPYRROLIDONE (NMP) as solvent, in mass ratio 80:12:8 weigh negative pole material respectively
Material, acetylene black and poly- inclined tetrafluoroethene（PVDF）, after ground and mixed is uniform, it is coated on pretreated Copper Foil, put into vacuum and do
It is dried to obtain positive plate at 80 DEG C in dry case.Simple metal lithium piece makees negative pole, and microporous polypropylene membrane Celgard 2325 is barrier film,
LB315[m（DMC）:m（EMC）:m（EC）=1:1:1] mixed solution as electrolyte, full of in argon glove box（H2O contains
Amount<1ppm）It is assembled into simulated battery.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery；
Under the conditions of test voltage 1.0～3.0V, the discharge and recharge of 0.1C, room temperature first discharge specific capacity is 158.4mAh/g, storehouse first
Human relations efficiency is 101.1%, and after 90 charge and discharge cycles, capability retention is 96.8%；In test voltage 1.0～3.0V, the charge and discharge of 5C
Under the conditions of electricity, room temperature first discharge specific capacity is 77.9mAh/g.
Embodiment 2
（1）Weigh the Li of example 1 preparation4Ti5O12White powder and polyvinyl alcohol (LTO：PVA=10:1) powder is put in beaker,
Appropriate distilled water heating for dissolving is added in polyvinyl alcohol.Again by poly-vinyl alcohol solution and Li4Ti5O12White powder is in mortar
Add a certain amount of water mix homogeneously, and be fully ground 1 hour until mixture becomes homogeneous rheology phase.
（2）Rheology phase is placed in air dry oven and is dried 10 hours under the conditions of 100 DEG C, to evaporate expeling moisture, obtain
To solid product；
（3）Solid product is placed in Muffle furnace and is calcined, programming rate is 5 DEG C/min, is warming up to 700 DEG C, calcining 1.5 is little
When；
（4）Grind 0.5 hour in mortar machine after being cooled to room temperature, that is, obtain described carbon-coated lithium ion battery negative material
Li4Ti5O12/C.
The negative material that embodiment 2 is obtained is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, with METHYLPYRROLIDONE (NMP) as solvent, in mass ratio 80:12:8 weigh negative pole material respectively
Material, acetylene black and poly- inclined tetrafluoroethene（PVDF）, after ground and mixed is uniform, it is coated on pretreated Copper Foil, put into vacuum and do
It is dried to obtain positive plate at 80 DEG C in dry case.Simple metal lithium piece makees negative pole, and microporous polypropylene membrane Celgard 2325 is barrier film,
LB315[m（DMC）:m（EMC）:m（EC）=1:1:1] mixed solution as electrolyte, full of in argon glove box（H2O contains
Amount<1ppm）It is assembled into simulated battery.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery；
Under the conditions of test voltage 1.0～3.0V, the discharge and recharge of 0.1C, room temperature first discharge specific capacity is 174.9mAh/g, storehouse first
Human relations efficiency is 104.4%, and after 50 charge and discharge cycles, capability retention is 97.6%；In test voltage 1.0～3.0V, the charge and discharge of 5C
Under the conditions of electricity, room temperature first discharge specific capacity is 94.2mAh/g.
Embodiment 3
（1）The preparation of rheology phase：Weigh nano titanium oxide and polyvinyl alcohol (TiO2：PVA=10:1) powder is put in beaker,
Appropriate distilled water heating for dissolving is added in polyvinyl alcohol.Again by poly-vinyl alcohol solution and nano titanium dioxide powder in mortar
Add a certain amount of water mix homogeneously, and be fully ground 0.5 ~ 1 hour until mixture becomes homogeneous rheology phase.
（2）The preparation of solid product：Rheology phase is placed in air dry oven and is dried 12 hours under the conditions of 100 DEG C, with
Moisture is driven away in evaporation, obtains solid product；
（3）Calcining：Solid product is placed in Muffle furnace and is calcined, programming rate is 5 DEG C/min, is warming up to 700 DEG C, calcining
1.5 hour；Grind 0.5 hour in mortar machine after being cooled to room temperature, that is, obtain described carbon encapsulated material TiO2/C.
（4）The covert preparation of Secondary Flow：By lithium carbonate, TiO2/ C is 2.025 in molar ratio: 5（Wherein in order to prevent height
A small amount of volatilization of lithium under warm environment, lithium carbonate excessive 5%）, after grinding to form fine particle respectively, mix homogeneously in big mortar, plus
Enter appropriate dehydrated alcohol, continue to grind 0.5 hour until mixture becomes homogeneous Secondary Flow covert.
（5）The preparation of secondary solid-phase product：Secondary Flow is in a disguised form placed in air dry oven and is dried 10 under the conditions of 100 DEG C
Hour, to evaporate expeling solvent, obtain secondary solid-phase product；
（6）Secondary clacining：Secondary solid-phase product is placed in Muffle furnace, in excess oxygen or air atmosphere under forged
Burn, programming rate is 5 DEG C/min, is warming up to 800 DEG C, calcine 10 hours, product is cooled to after room temperature and grinds 1 in mortar machine
Described carbon-coated lithium ion battery negative material Li is obtained after hour4Ti5O12/C.
The negative material that embodiment 3 is obtained is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, with METHYLPYRROLIDONE (NMP) as solvent, in mass ratio 80:12:8 weigh negative pole material respectively
Material, acetylene black and poly- inclined tetrafluoroethene（PVDF）, after ground and mixed is uniform, it is coated on pretreated Copper Foil, put into vacuum and do
It is dried to obtain positive plate at 80 DEG C in dry case.Simple metal lithium piece makees negative pole, and microporous polypropylene membrane Celgard 2325 is barrier film,
LB315[m（DMC）:m（EMC）:m（EC）=1:1:1] mixed solution as electrolyte, full of in argon glove box（H2O contains
Amount<1ppm）It is assembled into simulated battery.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery；
Under the conditions of test voltage 1.0～3.0V, the discharge and recharge of 0.1C, room temperature first discharge specific capacity is 172.1mAh/g, storehouse first
Human relations efficiency is 100.5%, and after 90 charge and discharge cycles, capability retention is 95.4%；In test voltage 1.0～3.0V, the charge and discharge of 5C
Under the conditions of electricity, room temperature first discharge specific capacity is 43.7mAh/g.
Embodiment 4
（1）Lithium carbonate, nano titanium oxide are in molar ratio 2.025: 5.05（Wherein in order to prevent lithium under hot environment
A small amount of volatilization, lithium carbonate excessive 5%）, after grinding to form fine particle respectively, mix homogeneously in big mortar.
（2）Weigh a certain amount of polyvinyl alcohol (Ti again：PVA=10:1) powder is put in beaker, adds suitable in polyvinyl alcohol
Amount distilled water heating for dissolving.Poly-vinyl alcohol solution and nano titanium oxide, lithium carbonate powder are added in mortar a certain amount of
Water mix homogeneously, and be fully ground 0.5 ~ 1 hour until mixture becomes homogeneous rheology phase.
（3）Rheology phase is placed in air dry oven and is dried 10～12 hours under the conditions of 80～120 DEG C, to evaporate expeling
Solvent, obtains solid product；
（4）Solid product is placed in Muffle furnace, in excess oxygen or air atmosphere under calcined, programming rate be 3
～8 DEG C/min, it is warming up to 800 DEG C, calcines 10 hours, product is cooled to after grinding 0.5～1 hour in mortar machine after room temperature
Obtain described carbon-coated lithium ion battery negative material Li4Ti5O12/C.
The negative material that embodiment 4 is obtained is assembled into CR2032 type button cell and carries out charge and discharge cycles test.Using
Coating method prepares electrode, with METHYLPYRROLIDONE (NMP) as solvent, in mass ratio 80:12:8 weigh negative pole material respectively
Material, acetylene black and poly- inclined tetrafluoroethene（PVDF）, after ground and mixed is uniform, it is coated on pretreated Copper Foil, put into vacuum and do
It is dried to obtain positive plate at 80 DEG C in dry case.Simple metal lithium piece makees negative pole, and microporous polypropylene membrane Celgard 2325 is barrier film,
LB315[m（DMC）:m（EMC）:m（EC）=1:1:1] mixed solution as electrolyte, full of in argon glove box（H2O contains
Amount<1ppm）It is assembled into simulated battery.Carry out constant current cycle charge discharge electrical testing with LAND battery test system button type battery；
Under the conditions of test voltage 1.0～3.0V, the discharge and recharge of 0.1C, room temperature first discharge specific capacity is 166.2mAh/g, storehouse first
Human relations efficiency is 109.4%, and after 90 charge and discharge cycles, capability retention is 94.3%；In test voltage 1.0～3.0V, the charge and discharge of 5C
Under the conditions of electricity, room temperature first discharge specific capacity is 42.9mAh/g.
Claims (6)
1. the preparation method of carbon-coated lithium ion battery negative material, is characterized in that step is as follows：
（1）The preparation of rheology phase：By lithium salts：Titanium dioxide in molar ratio 4.05～4.15：5～5.05 take material, mix homogeneously,
Add lithium salts and titanium dioxide gross mass in 3%～6% solvent, grind pulp together, obtain rheology phase；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in air dry oven, dry under the conditions of 80～120 DEG C
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）The preparation of presoma：Solid product is placed in Muffle furnace and is calcined, programming rate is 5 DEG C/min, is warming up to
400～600 DEG C, calcine 4～6 hours, obtain presoma；
（4）The preparation of negative material：Presoma is cooled to and grinds 0.5～1 hour in mortar machine after room temperature, after grinding before
Drive body compacting after be placed in Muffle furnace, in excess oxygen or air atmosphere under calcined, programming rate be 3～8 DEG C/
Min, is warming up to 600～900 DEG C, calcines 6～10 hours, the lithium ion battery negative material obtaining after being cooled to room temperature
Li4Ti5O12；
（5）The covert preparation of Secondary Flow：By step（4）Obtained negative material Li4Ti5O12With carbon source according to mass ratio 10～
10.15:1～1.25 mix homogeneously, is subsequently added Li4Ti5O12With the solvent of carbon source gross mass 5%～10%, grind to form together
Pulpous state, obtains Secondary Flow covert；
（6）The preparation of secondary solid-phase product：By step（5）Gained Secondary Flow is in a disguised form placed in air dry oven in 80～120 DEG C
Lower drying 10～12 hours, to evaporate expeling solvent, obtains secondary solid-phase product；
（7）Secondary clacining：By step（6）Gained secondary solid-phase product is placed in Muffle furnace to be calcined, programming rate be 5 DEG C/
Min, is warming up to 600～800 DEG C, calcines 1～2 hour, product is cooled to after room temperature and grinds 0.5～1 hour in mortar machine,
Obtain final product described carbon-coated lithium ion battery negative material Li4Ti5O12/C.
2. the preparation method of carbon-coated lithium ion battery negative material, is characterized in that step is as follows：
（1）The preparation of rheology phase：Take titanium dioxide and carbon source according to mass ratio 10～10.15:1～1.25 feeding, mix homogeneously,
Add the solvent of titanium dioxide and carbon source gross mass 3%～6%, grind pulp together, obtain rheology phase；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in dry under the conditions of 80～120 DEG C in air dry oven
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）Calcining：By step（2）Gained solid product is placed in Muffle furnace to be calcined, and programming rate is 5 DEG C/min, heats up
To 600～800 DEG C, calcine 1～2 hour, product is cooled to after room temperature and grinds 0.5～1 hour in mortar machine, obtain final product carbon bag
Cover material TiO2/C；
（4）The covert preparation of Secondary Flow：Molal quantity by lithium in lithium salts：Carbon encapsulated material TiO2/ C mol ratio is 4.05～4.15:
5～5.05 mix homogeneously, add lithium salts and carbon encapsulated material quality in 3%～6% solvent, grind pulp together, obtain two
Secondary rheology phase；
（5）The preparation of secondary solid-phase product：Rheology phase is placed in air dry oven and is dried 10～12 under the conditions of 80～120 DEG C
Hour, to evaporate expeling solvent, obtain secondary solid-phase product；
（6）Secondary clacining：Secondary solid-phase product is placed in Muffle furnace, in excess oxygen or air atmosphere under forged
Burn, programming rate is 3～8 DEG C/min, is warming up to 600～900 DEG C, calcine 8～16 hours, product is cooled to after room temperature and is grinding
Described carbon-coated lithium ion battery negative material Li is obtained after grinding 0.5～1 hour in alms bowl machine4Ti5O12/C.
3. the preparation method of carbon-coated lithium ion battery negative material, is characterized in that step is as follows：
（1）The preparation of rheology phase：In molar ratio 4.05～4.15:5～5.05：0.05 by the molal quantity of the lithium of lithium salts, titanium dioxide
Titanium and carbon source mix homogeneously, add reactant gross mass in 3%～6% solvent, grind pulp together；
（2）The preparation of solid product：By step（1）Gained rheology phase is placed in dry under the conditions of 80～120 DEG C in air dry oven
Dry 10～12 hours, to evaporate expeling solvent, obtain solid product；
（3）Calcining：By step（2）Gained solid product is placed in Muffle furnace, in excess oxygen or air atmosphere under carry out
Calcining, programming rate be 3～8 DEG C/min, be warming up to 600～900 DEG C, calcine 8～16 hours, by product be cooled to after room temperature
Described carbon-coated lithium ion battery negative material Li is obtained after grinding 0.5～1 hour in mortar machine4Ti5O12/C.
4. as described in one of claim 1-3 carbon-coated lithium ion battery negative material preparation method, it is characterized in that：Described molten
Agent is water, ethanol or propanol.
5. as described in one of claim 1-3 carbon-coated lithium ion battery negative material preparation method, it is characterized in that：Described carbon
Source is one of polyvinyl alcohol, carbamide, sucrose or citric acid.
6. as described in one of claim 1-3 carbon-coated lithium ion battery negative material preparation method, it is characterized in that：Described lithium
Salt is one kind of lithium nitrate, lithium carbonate or Lithium hydrate.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108306012A (en) * | 2018-01-30 | 2018-07-20 | 郑州中科新兴产业技术研究院 | A kind of anti-flatulence lithium titanate material of high magnification and preparation method thereof |
| CN110112418A (en) * | 2019-06-12 | 2019-08-09 | 河北师范大学 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries meterial additive |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391806A (en) * | 2007-09-20 | 2009-03-25 | 北京有色金属研究总院 | Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material |
| CN102945952A (en) * | 2012-12-05 | 2013-02-27 | 吉林大学 | Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries |
| CN103022462A (en) * | 2012-12-20 | 2013-04-03 | 中国东方电气集团有限公司 | Preparation method for high-conductivity lithium titanate cathode material of lithium battery |
-
2016
- 2016-12-09 CN CN201611127237.1A patent/CN106486662A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101391806A (en) * | 2007-09-20 | 2009-03-25 | 北京有色金属研究总院 | Method for manufacturing spinelle lithium titanate for lithium ionic cell cathode material |
| CN102945952A (en) * | 2012-12-05 | 2013-02-27 | 吉林大学 | Method for preparing anode material carbon coated lithium titanate for lithium ion power batteries |
| CN103022462A (en) * | 2012-12-20 | 2013-04-03 | 中国东方电气集团有限公司 | Preparation method for high-conductivity lithium titanate cathode material of lithium battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108306012A (en) * | 2018-01-30 | 2018-07-20 | 郑州中科新兴产业技术研究院 | A kind of anti-flatulence lithium titanate material of high magnification and preparation method thereof |
| CN110112418A (en) * | 2019-06-12 | 2019-08-09 | 河北师范大学 | A kind of preparation method of silicon/carbon/graphite in lithium ion batteries meterial additive |
| CN112919434A (en) * | 2021-02-09 | 2021-06-08 | 复旦大学 | Carbon-rich carbonitride as negative electrode material of secondary battery, and preparation method and application thereof |
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